Liquid explosive compositions of hydrogen peroxide and an aromatic sulforic acid and process for the preparation thereof

ABSTRACT

The present invention relates to liquid explosives comprising hydrogen peroxide and aromatic sulfonic acid and also liquid or gel explosives containing, in addition to hydrogen peroxide and aromatic sulfonic acid, organic plasticizer, gelling agent, inorganic oxidizer salt, metal powder etc. These explosive compositions have a strong explosive power and they are suitable for various purposes by mixing them instantly at a blasting site.

United States Patent Yokogawa et a1.

[ 1 Apr. 30, 1974 LIQUID EXPLOSIVE COMPOSITIONS OF HYDROGEN PEROXIDE AND AN AROMATIC SULFORIC ACID AND PROCESS FOR THE PREPARATION THEREOF Inventors:

Assignee:

Filed:

Appl. No.:

US. Cl. 149/40, 149/109 Int. Cl C06b 15/00 Field of Search 149/40, 109

Mutsuo Yokogawa; Shiro Mitsui; Yoshiyuki Ikeda, all of Yamaguchi-ken, Japan Nippon Kayaku Kabushiki Kaisha,

Tokyo, Japan Dec. 8, 1972 References Cited UNITED STATES PATENTS 9/1969 Bronstein 149/40 X 3,047,441 7/1962 Baker 149/109 3,687,746 8/1972 Bieber et al. 149/109 X 3,095,334 6/1963 Scurlock 149/40 X 3,574,011 4/1971 Knight 149/40 X 3,645,809 2/1972 Stow 149/40 X Primary ExaminerCarl D. Quarforth Assistant ExaminerE. A. Miller Attorney, Agent, or Firm-Russell & Nields 1 ABS'I RACT 6 Claims, No Drawings RECEIVER FOR FACSIMILE SYSTEM The present invention-relates to faximile system and -more particularly to an improved faximile system which converts a faximile signal into successive runlength" binary code signals, transmits the successive run-length binary-code signals, and reconverts'the runlength binary code signals into the original faximile signal.

A faximile system generally includes a transmitter for converting a photographic image carried on an information medium such as paper into an electric image signal, that is, a faximile signal and for transmitting the faximile signal, and a receiver for receiving the transmitted faximile signal and for reconverting the faximile signal into the original photographic :image. Since the faximile signal usually consists of space (white) and vide an improved faximile system which iseconomical.

It is another object of the present invention to provide an improved faximile system including an .improved receiver which is capable of correctly .decoding transmitted code signals in spite of the fluctuations of the code signals due to the impedance of the transmission line.

These and other objects and the attendant advantage-s of the invention will become more readily appreciated .as the same becomes better understood by reference to the following detailed description when taken in conjunction with the accompanying drawings in which:

FIG. 1 is a diagram showing a waveform of a-faximile signal.

FIG. 2 is a diagram showing successive binary code signals'representing the faximile signal of FIG. 1.

FIG. 3 is a table showing a coding system employed for the faximile system of the invention.

FIG. 4A is a diagram showing an information medium.

FIG. 4B is a diagram showing waveforms produced by .scanning with a light-spot the information medium of FIG. 4A.

FIG. 4C is a diagram showing a waveform of a faximile signal transmitted from a transmitter of the faximile system of the invention.

FIGS. 5, 6a and 6b are block diagrams of a transmitter of a faximile system of the invention.

FIG. 7A .is a diagram showing an .information medium to be processed by the transmitter of FIGS. and 6.

FIG. 7B is a diagram showing a waveform of a fax- .imile'signal produced by the photo-electric converter of FIG. 5.

FIGS. 7C, 7D and 7E are diagrams showing waveforms of signals appearing in the transmitter of FIGS.

5 and 6.

FIGS. 8A through 8D are diagrams showing waveforms of signals appearing in the transmitter-of FIGS. 5 and 6.

FIGS. 9A through 9P are diagrams showing waveforms of signals appearing in the transmitter of FIGS. 5 and 6.

FIG. 10 is a diagram for the explanation'of'the opera tion of a coding portion of the transmitterof FIGS. 5 and 6.

FIGS. 11A through 11E are diagrams showing waveforms of signals appearing in the transmitter of FIGS. 5 and 6.

FIGS. 1.2a and 12b are schematic block diagrams showing a receiver according to the invention.

FIGS. 13A through 13M, and 14A through 14D are diagrams showing waveforms of signals appearing in i the receiver of FIG. 12.

FIG. 15 is a block diagram of a part of the receiver of FIG. 12.

FIGS. 16A through 16L are diagrams showing waveforms of signals appearing in the receiver of FIG. 12.

Referring now to the drawings and more specifically to FIG. 1 thereof, there is illustrated a waveform of a faximile signal of 1H which is, namely produced by once horizontally scanning with alight spot an information medium carrying thereon photographic image in the form of letters or figures. It is, in this instance, assumed that the total width of the 1H faximile signal is equal to 98 unit times and mark and space signals of the faximile signal respectively have such widthes as indicated by numerals on the basis of the particular unit time. It is now to be noted that the width of the mark or space signal is usually called run-length.

In FIG. 2, there is shown successive binary code signals respectively representing the run-length of the mark and space signals in the faximile signal shown in FIG. 1. The binary code signal of FIG. 2 is based on a binary coding system as shown in a table of FIG. 3. As shown in FIG. 2, the total bits of the binary code signals are merely 36 and it is accordingly apparent that the transmission interval can be extremely reduced by transmitting the faximile signal in the form of binary code signals.

The coding system shown in the table of FIG. 3 will be explained hereinbelow.

When a run-length (n) of an either mark or space signal is equal to or larger than 3 (n a 3), the binary code representing the run-length (n) consists of lower figure binary digits representing n l and higher figure digits of one or more Os the number of which equals to (the number of figure of the binary digits. of lower figure 1). When, for example, n equals to 15 (n 15), the lower figure digits are given by 1 n 1 14. (decimal) 1110 (binary).

Since the number of figure of the lower digits equals to 4, the higher figure digits are 000. Accordingly, when n 15 the binary code according to the particular system is expressed as O 0 0 l l l 0 (higher) (lower) When n l and n 2, the corresponding binary codes are otherwise defined as follows:

This coding system is advantageous in that a binary code according to the coding system is shorter in time than that of the corresponding run-length except that n l, 2, 3, or 5. When, for example n =100, the corresponding binary code is shorter than the run-length by a rate of 13/100 (=1/7.7). When n 500, the corresponding binary code is shorter than the run-length by a rate of 17/500 (1/29.4).

It is now to be understood that the above-mentioned coding system is effective for reducing the transmission interval for space information between lines, letters or the like.

When such photographic image information carried on an information medium as shown in FIG. 4A is scanned along lines p q p q p q and p q 4, faximile signals p,q,', p 'q p 'q and p 'q are produced in the transmitter, which faximile signals consist of space signals S S S and mark signals M M M respectively having run-length indicated by parenthesized numerals. The faximile signals are then converted into successive binary code signals are shown in FIG. 4C, wherein pulses V are vertical synchronizing pulses separating the binary code signals each corresponding to a faximile signal of 1-H.

ln FIGS. 5 and 6, there is shown a transmitter of a faximile system according to the invention, which generally comprises a faximile signal generator for producing a faximile signal representing photographic image information, a pulse generator 11 for producing a clock pulse signal, a horizontal synchronizing pulse signal and blanking pulse signal, a carrier wave genera- -tor 12 for producing carrier waves, a sampler 13 for sampling the faximile signal from the faximile signal generator 10 with the clock pulse signal, a coder 14 for coding the sampled faximile signal into successive binary code signals, and a modulator 15 for modulating a carrier wave with the binary code signals. The faximile signal generator 10 includes a fibre optics cathode-ray tube having a fibre optics faceplate 21 and a horizontal deflection element 22. A horizontal deflection circuit 23 produces a horizontal deflection signal in accordance with a horizontal synchronizing pulse signal from the pulse generator 11. A feed means 24 such as a pair of rollers feeds an information medium 25 carrying thereon image information to be picked up in close proximity to the fibre optics faceplate 21. The feed means 24 is actuated by a prime mover 26 such as an electric pulse motor which is driven by a driver 27 when the driver 27 is energized by a vertical synchronizing pulse signal generated in the sampler 13. A photo-electric converter 28 is positioned in the vicinity of the fibre optics faceplate 21, the converter 28 converts the light-spot modulated by the image information into an electric signal, that is, a faximile signal.

The sampler 13 includes a first binary counter 30 having a trigger input terminal connected to an output of a first AND gate 31 and a clear input terminal connected to an output of a first OR gate 32. Output terminals of the first binary counter 30 are connected to first group input terminals of a coincident circuit 33. The coincident circuit 33 further has second group input terminals connected to output terminals of a second binary counter 34 which has a trigger input terminal connected to an output of a second AND gate 35, and a clear input terminal connected to an output terminal of a vertical synchronizing pulse signal generator 36. The second binary counter 34 has an overflow output terminal through which an overflow signal is produced when the second binary counter 34 overflows. The overflow output terminal is connected to one input of a second OR gate 37 and an input terminal of the vertical synchronizing pulse signal generator 36. The coincident circuit 33 is adapted to produce a coincident signal on an output terminal thereof connected to a set terminal of a first flip-flop circuit 38 and an input terminal of a mark-space signal controller 39. The first flip-flop circuit 38 has a reset terminal connected to an output of the second OR gate 37 and an output terminal connected to one input of the second AND gate 35. The other input of the second AND gate 35 is connected to a clock pulse terminal of the pulse generator 11. The other input of the second OR gate 37 is connected to an output terminal of the mark-space signal controller 39 which has three other input terminals respectively connected to the faximile signal generator, the clock pulse terminal of the pulse generator 11 and an output terminal of a second flip-flop circuit 40. A reset terminal of the second flip-flop circuit 40 is connected to an output terminal of the vertical synchronizing pulse generator 36. The output terminal of the generator 36 is further connected to an input terminal of the driver 27 and to one input of a third OR gate 41 which has an output connected to a set terminal of a third flip-flop circuit 42. A reset terminal of the third flip-flop circuit 42 is connected to a horizontal synchronizing pulse terminal of thepulse generator 11. An output terminal of the flip-flop circuit 42 is connected to one input of the first AND gate 31 the other input of which is connected to the clock pulse terminal of the pulse generator 11. One input of the first OR gate is connectedv to the output terminal of the vertical synchronizing pulse generator 36.

The coder 14 includes an 1 bit eliminator 50 having an input terminal connected to the output of the second AND gate 35. An output terminal of the 1 bit eliminator 50 is connected to an input terminal of a binary counter 51 having output terminals connected to input terminals of a bit number identify matrix 52 and a parallel in-series out shift register 53. A clear input terminal of the binary counter 51 is connected to an output terminal of a clear pulse generator 54. Output terminals of the bit number identify matrix are connected to input terminals of a coding matrix 55. The parallel in series out shift register 53 has a trigger input terminal connected to a write pulse generator 56 and a clear input terminal connected to the output terminal of the clear pulse generator 54. The write pulse generator 56 has input terminals respectively connected to the output terminal of the first flip-flop circuit 38 and to the clock pulse terminal of the pulse generator 11. Output terminals of the shift register 53 are connected to input terminals of the coding matrix 55 which has a coding completion signal terminal connected to one input terminal of the clear pulse generator 54 and to input terminals of the first and second OR gates 32 and 41 of the sampler 13. The coding completion signal terminal of the coding matrix is further connected to a trigger terminal of the second flip-flop circuit 40 of the sampler 13. The other input terminal of the clear pulse generator 54 is connected to the overflow terminal of the binary counter 34 of the sampler 13. The shift register 53 has a clear input terminal connected to the output terminal of the clear pulse generator 54 and a shift pulse input terminal connected to an output terminal of a shift pulse generator 57 which has'input terminals connected to the horizontal synchronizing pulse termiconverted completely to nonexplosive ones by adding more than nearly the equivalent quantity of water thereto. Accordingly, any misfired explosive which remains after the explosion or any leaked explosive may ample, aluminum powder, magnesium powder, aluminum/magnesium alloy powder as assistant reducing agents. Quantities of these assistant oxidizing agents and assistant reducing agents are desirably 5 30 be treated easily and completely by pouring water 5 percent by weight and l 10 percent by weight, respecthereon. tively, based on the total composition. With a smaller Said liquid explosive compositions can be converted quantity, the effect of the incorporation is poor and to gel form by adding a proper quantity of a suitable with a larger quantity, the explosive power is decreased water-soluble gelling agent such as polyvinyl'alcohol, and the explosive becomes impracticable. guar gum, carboxymethyl cellulose or methyl cellulose. 10 Said additives may be mixed with the liquid compo- Viscosity of the compositions can be controlled suitnents of the invention in the same manner as in the case y of the water-soluble gelling agent. The inorganic oxi- By the addition of the water-soluble gelling agent, the dizer salts are mixed previously with the aqueous hyexplosive power of the compositions is inclined to be drogen peroxide solution to obtain a solution. The reduced in some degree. If the gelling agent is incorpometal powders are mixed previously with the waterrated in an excessive quantity, the adhesive property of soluble gelling agent. Thus, the composition can be the product is damaged. The preferred quantity of the prepared readily at a blasting site in the same manner gelling agent is less than 10 percent by weight of the as in said case of using of a water-soluble gelling agent total composition. For obtaining an efficient viscosity, as an additive. If the metal powder is to be incorpoincorporation of more than 2 percent by weight of the rated, it is most preferred to use the water-soluble gelgelling agent is desirable- Thus the above comPositions ling agent together with it in order to facilitate homogecan be adhered to the surface of an object to be blown neous dispersion of the metal powder in the explosive up, taking advantage of their adhesive property, or they composition. can be inserted into horizontal or upward bore holes, The present invention will be illustrated bYiviTydfEi taking advantage of their adhesive property as in the amples. case of general gell explosives. ln Example 1, proportion of aqueous hydrogen pet- The gel explosives may be prepared by merely mixing oxide solution to aromatic sulfonic acid was deterthe liquid component with the gelling agent in a suitmined so as to satisfy stoichiometric oxygen balance for able vessel. If the gel explosive is to be prepared at a exhibiting the maximum explosive power. Of course, as blasting site, aqueous hydrogen peroxide solution in in usual explosives, the proportion may be changed one container and a fuel comprising aromatic sulfonic freely to shift the oxygen balance in or direcacid or a mixture of aromatic sulfonic acid and organic tion. In this connection, it is to be noted that, if hydroplasticizer in another container are poured into a widegen peroxide content is reduced, explosive power of mouth bottle containing water-soluble gelling agent dithe composition is reduced. For example, in No. l in rectly before the use. Each of the components may be Example l, hydrogen peroxge content X transported in said containers, respectively. Thus, the 100 69.3 (percent by weight) and detonation vecomponents can be transported safely without fear of locity is 8,300m/sec., while in No. 8, hydrogen peroxexplosion, and the desired explosive can be prepared ide content is lower (85.0 X l00=5l.0 percent by dil weight) and therefore, detonation velocity is also lower Of course, it is possible to control the explosive prope-)- If EXAMPLE 1 Composition, percent Properties Naphtha- Anthra- Nitro- Detona- Aqueous hydrogen peroxide solution Benzene- Toluenelenequinone phenoltion sulfonic sulfonic sulfonic sulfonic sulfonic Specific velocity Brisance Numbel 90 80 70 60 acid acid acid acacid gravity (m./sec.) (m./m.)

1 By weight.

N ote.-Detonation velosity was determined according toDautriche detonation velocity-determining method of Davis described on page 17 of Chemistry of Powder and Explosives." Brisanee was letermined according to said Hess method.

hydrogeiperoiii decontent iri tlie wliole composition-i;

less than 40 percent by weight, initiation of the composition becomes difficult.

Although only five aromatic sulfonic acids are shown in this example, the other aromatic sulfonic acids suchas xylenesulfonic acid and phenolsulfonic acid may be used too.

ticizer and water soluble gelling agent was selected so The explosive compositions in this example were prepared simply by weighing aqueous hydrogen peroxide solution and aromatic sulfonic acid in separate vessels, pouring the aromatic sulfonic acid into the vessel of ple I. Said proportion may be altered freely. However, if hydrogen peroxide content is less than 40 percent by weight, initiation of the composition becomes difficult as mentioned in Example 1.

aqueous hydrogen peroxide solution and shaking the Although only two typical concentrations of aqueous mixture lightly to obtain homogeneous mixture directly hydrogen peroxide solution, two typical aromatic sulbefore the use. fonic acids and two typical organic plasticizers are In Example 2, too, proportion of aqueous hydrogen shown in this example, other concentrations higher peroxide solution, aromatic sulfonic acid and organic n 60 percent by weight of the aqueous hydrogen plasticizer was determined so as to satisf stoichiometperoxide solution, other aromatic sulfonic acids such as ric oxygen balance. Said proportion may be altered benzenesulfonic acid and other organic plasticizers freely. However, it is to be noted that, if hydrogen ersuch as tricresyl phosphate may be used, too, described oxide content in the whole composition is less than 40 above. In addition to the above three water soluble gel- .percent by weight, initiation of the composition beling agents, carboxymethyl cellulose may be used. comes difficult as mentioned in Exam le 1.

Although only four typical aromati c: sulfonic acids PROCESS FOR THE PREPARATION OF and only four typical organic plasticizers are shown in EXPLOSIVE IN THIS EXAMPLE this example, other aromatic sulfonic acids such as xy- Aqueous hydrogen peroxide solution was mixed with lenesulfoniC acid and PheIlOlSUlfOniC i a h r aromatic sulfonic acid or with mixture of aromatic sulganic plasticizers such as dibutyl phthalate and butylallyl phthalate may be used, too.

in this example, the explosive compositions were prepared by mixing aromatic sulfonic acid with organic plasticizer under heating at 90 C and then dissolving the mixture in aqueous hydrogen peroxide solution weighed and placed previously in another vessel.

in Example 3, too, proportion of aqueous hydrogen peroxide solution, aromatic sulfonic acid, organic plasas to satisfy stoichiometric oxygen balance as in Examfonic acid and organic plasticizer in the same manner as in Example 1 or 2 to obtain liquid composition. Thus resulting composition was added to water soluble gelling agent weighed previously in a wide mouth vessel and the whole was stirred to obtain gel explosive composition.

In Example 4, proportion of aqueous hydrogen peroxide solution, aromatic sulfonic acid, organic plasticizer, water soluble gelling agent, water-soluble inorganic oxidizer salt and metal powder was selected so as to satisfy stoichiometric EXAMPLE 2 Composition, percent Aromatic sulfonic acids Organic plasticizers Properties Aqueous hydrogen Ben- Tol- Naph- Anthra- Dibu- 'Iri- Detonaperoxide solution zeneuenethalenequinone- Dioctyl toxycresyl tion sulfonic sulfonic sulfonic sulionie Dimethyl phthalethyl- DllOS- Specific velocity Brisnncc Number 90 80 70 acid acid acid acid phthalate ate adipate phatc gravity (nu/sec.) (UL/ill.)

1. 38 7, 800 21. 0 1.40 7,300 10.8 1. 36 7. (S00 13. J 1. 40 17. 0 1.30 5, 000 11.3 1. 24 4, 500 El. 3 1. 2i) 3, 300 (l. l)

Note-Detonation velocity and brlsuneo were determined in the some manner as in Example 1.

EXAMPLE 3 Composition, percent Aqueous hydrogen peroxide solution Aromatic sulfonic acid Organic plasticizer Water-soluble gelling agent Properties Naphtha- Detona- Toluenelenetion sulfonic sulfonic Dimethyl Dioctyl Polyvinyl Methyl Guar Specific velocity Brisa ce Numbez 90 acid acid phthalate phthalate alcohol cellulose gum gravity (rm/sec.) (m./m.)

Note-Detonation velocity and brisance were determined in the same manner as in Example 1.

EXAMELE 4 Composition, percent Water-soluble Aromat c Watcrinorganic oxidizer Properties Aqueous sulfonic Organic soluble salts Metal powders hydrogen acid, plastigelling Detonaperoxide toluenecizer, diagent, Ammo- Lithium Alu- Magnetion solution, sulfonic methyl polyvinyl nium perminum slum Specific velocity 13 risanee Number acid phthalate alcohol nitrate chlorate powder powder Water gravity (m./sec.) (m./m.)

80.0 1.13 5, 500 13. 8 62. 0 1. 50 (l, 000 15. 3 60.0 1.10 400 13.0 82. 0 1 25 5, ll). 7 80.0 1 ()u 3, 900 7. x

Note-Detonation velocity and brlsancc were determined in the same manner as in Example 1.

oxygen balance as in Example I. Said proportion may be altered freely. However, if hydrogen peroxide content in the whole composition is less than 40 percent by weight, initiation of the composition becomes difficult, as mentioned in Example 1.

ln Nos. 4 and 5, 20 percent, based on the gross amount, of water was added to the oxygen-balanced composition comprising aqueous hydrogen peroxide solution and fuel to reduce the explosive power to a desired value. Thus, a composition prepared by using aqueous hydrogen peroxide solution of high concentration may be reduced in its power to a desired value by the addition of water.

Although only some typical concentrations of aqueous hydrogen peroxide solution, aromatic sulfonic acids, organic plasticizers and water soluble gelling agents are shown in this example, other varieties of them may be used, of course, as described in Examples 1, 2 and 3. As water-soluble inorganic oxidizer salt, there may be used also sodium nitrate, barium perchlorate, etc. As metal powder, aluminum-magnesium alloy powder may be used.

PROCESS FOR THE PREPARATION OF EXPLOSIVE IN THIS EXAMPLE Compositions Nos. 1, 2 and 3 were obtained by charging aqueous hydrogen peroxide solution or a mixture of aqueous hydrogen peroxide solution and watersoluble inorganic oxidizer salt in one vessel, and dissolving aromatic sulfonic acid or-a mixture of aromatic sulfonic acid and organic plasticizer in above solution directly before the use to obtain liquid composition.

Liquid explosive composition No. 2 was thus obtained. The compositions Nos. 1 and 3 were obtained by adding said liquid explosive composition to a mixture of water soluble gelling agent and a metal powder weighed and placed in a wide mouthed-vessel previously and then stirring the whole mixture to obtain gel explosive composition. Compositions Nos. 4 and 5 were obtained by previously preparing an explosive composition comprising mixture of aqueous hydrogen peroxide solution and fuel in the same manner as in Examples l, 2 and 3 or the above Nos. 1, 2 and 3 and then adding a suitable quantity of water thereto to obtain explosive of low explosive power.

50 Grams of product No. 3 in Example I packed in a polyethylene film bag were used as a booster of slurry explosive. Detonation velocity of the slurry explosive as compared with that of using conventional pentolite as a booster is shown in the following table. The explosvie charged in a steel pipe of 50m/m inside diameter and set off to determine its detonation velocity.

Kind of Booster Detonation Velocity Product No. 3 in Example 4,870 m/sec.

Pentolite (50g) 4,790 m/sec.

5 Thus, the explosive compositions of the invention can be used as booster which can be prepared readily in a field of blasting.

What is claimed is:

1. An explosive composition comprising a mixture of an aqueous hydrogen peroxide solution of a concentration higher than 60 percent by weight, the hydrogen peroxide being more than 40 percent by weight of the explosive composition, and an aromatic sulfonic acid.

2. An explosive composition comprising a mixture of an aqueous hydrogen peroxide solution of a concentration higher than 60 percent by weight, the hydrogen peroxide being more than 40 percent by weight of the explosive composition, an aromatic sulfonic acid, and one or more materials selected from the group consisting of organic plasticizers, water-soluble gelling agents, inorganic oxidizer salts and metal powders.

3. Explosive composition as set forth in claim 1 comprising a mixture of an aqueous hydrogen peroxide solution of a concentration higher than 60 percent by weight, the hydrogen peroxide being 40 82 percent by weight of the explosive composition, and an aromatic sulfonic acid being 3 30 percent by weight of said' composition.

4. Explosive composition as set forth in claim 2 comprising a mixture of an aqueous hydrogen peroxide so lution of a concentration higher than 60 percent by weight, the hydrogen peroxide being 40 82 percent by weight of the explosive composition, an aromatic sulfonic acid being 3 30 percent by weight of said com-,

position, and one or more materials selected from the group consisting of organic plasticizer of the weight ratio 1 0.1 l 3 versus said aromatic sulfonic acid, water soluble gelling agent being 2 10 percent by .weight of said composition, inorganic oxidizer salt being 5 30 percent by weight of said composition and metal powder being 1 10 percent weight of said composition.

5. Process for preparing an explosive which coinprises heating an organic plasticizer preliminarily to the temperature range 70 100 C and mixing an aromatic sulfonic acid therewith and then mixing the thus obtained mixture with aqueous hydrogen peroxide sooxidizer salt and metal powder.

Patent Nu. 3 8,0 2 Dated April 30, 1974 Inventods) Mutsoo Yokogawa et a1,

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Cancel the original columns 1 through 4 and substitute the corrected columns as shown on the attached sheet.

Signed and sealed this 10th day of September 1974.

(SEAL) Attest:

MCCOY M. GIBSON, 'JR. (3. MARSHALL DANN Attesting Officer Commissioner of Patents FORM PO'IOSO (10-69) USCOMM-DC 60376-P69 Q U.S. GOVERNMENT PRINTING OFFICE: [969 0-866-33L i LIQUID EXPLOSIVE COMPOSITIONS OF HYDROGEN PEROXIDE AND AN AROMATIC SULFONIC ACID AND PROCESS FORTHE PREPARATION THEREOF DETAILED DESCRIPTION OF THE iv INVENTION The present invention relates to liquid or gel explosives containing an aqueous hydrogen peroxide been used, since they have some defects with respect to properties and safety. If appropriate liquid explosives can be developed, a new field of use of explosives may be expected, since liquid has excellent properties such as free fluidity and the property close filling.

From this point of view, the inventors have developed liquid explosives which can be prepared in the field by a simple mixing means and which can be handled safely, and gel explosives containing the liquid explosives as a main ingredient.

The explosives of the present invention can be used for blasting for various purposes owing to their characteristic, i.e., free fluidity and the property of close filling. They may be packed in a given container Further, making the best use of their characteristic features, i.e., easy preparation thereof by a simple mixing operation, high specific gravity and strong explosive power, they can be used safely as a booster of AN-FO explosives and slurry explosives prepared 40 at a blasting site.

It has been known that a liquid mixture prepared by dissolving an organic compound such as methanol,

. glycerol or acetone in an aqueous hydrogen peroxide solution of a high concentration has an explosive power. However. such a liquid mixture has not been used as a practical explosive due to the following defects:

.. e tarsaasantiu f heat s ate at h time of mixing, so the preparation of a large quantity therel of is dangerous.

,. Th myaa ssivs;iaxelxss 92 hazard due to its high sensitivity.

3. The decomposition of t h e explosive mixture starts at a re l atively low temperature and, Therefore,

it has a hazard of explosion by accumulated heat. 4.- hesxn s rshasaatmstermat ,erty and its power is reduced remarkably within abifit one week after preparation.

For the purpose of obtaining practical liquid explosive compositions by overcoming the above defects, the inventors have found that aromatic sulfonic acids and mixtures of aromatic sulfonic acids and organic plasticizers are optimum reducing agents (after'investigation of various organic com- P nd .-rar at ixmersan d .cqtn'aq mqs reducing agents soluble in aqueous hydrogen peroxide solution of a high concentration) and do not inhibit 2 stability of the concentrated aqueous hydrogen peroxide solution.

It is considered that the aromatic sulfonic acids are stable in hydrogen peroxide, since they are acidic in the solution due to their sulfonic acid groupand since they have a benzene nucleus.

Compositions of the present invention and conventional explosive compositions containing aqueous hydrogen peroxide solution of a high concentration 0 as the main oxidizing agent are shown in Table 1.

In each compositiomproportion of oxidizing agent to reducing agent is determined so as to satisfy its stoichiometric oxygen balance.

Benzenesulfonic acid, toluenesulfonic acid, naphthalene-sulfonic acid and anthraquinonesulfonic acid in Nos. 1-4 in Table are representative arofor blasting use for cutting of pipes and steel plates. 35

matic sulfonic acids of the present invention. There may be used in the same manner other aromatic sulfonic acids such as xylenesulfonic acid, phenolsulfonic acid, cresolsulfonic acid, benzenedisulfonic acid, benzenetrisulfonic acid, nitrobenzenesulfonic acid, nitrophenosulfonic acid, nitrotoluenesulfonic acid and nitroxylenesulfonic acid.

Dimethyl phthalate and dioctyl phthalate used together with aromatic sulfonic acid reducing agents in Nos. 5 and 6 in Table i are representative organic plasticizers of the invention. There may be used in, the same manner other organic plasticizers such as dibutyl phthalate, butylallyl phthalate, butylacrylbutyl glycol, tricresyl phosphate, butylbenzyl phthalr ty scba a si iti txlss zasata thsx sthy phthalate, dibutoxyethyl phthalate, dioctyl adipate, dibutoxyethyl adipate and dioctyl azelate.

According to the invention, the explosive compositions can be prepared on a large commercial scale, since aromatic sulfonic acids and mixtures of aromatic sulfonic acids and organic plasticizers are soluble in aqueous hydrogen peroxide solution without generation of heat.

In general, powerful explosive compositions can be obtained in a simple manner by mixing the components directly before use, since the aromatic sulfonic acid or the mixture of aromatic sulfonic acid and organic plasticizer is easily soluble in con centrated aqueous hydrogen peroxide solution.

The concentrated aqueous hydrogen peroxide solution and main fuels can be transported or handled Drop hammer sensitivities and decomposition temperatures of the explosive compositions 'of Table 1 the main reducing agent'or as one of the main reducing l are shown in Table 2 TABLE 2 v by weight of the total composition. If the aromatic 'sulfonic acid is too small in quantity, it is difficult to HFP Demmlmm" initiate the-resulting compostion and its explosive .No. Sens1t1v1ty temperature 5 t J power 1s very poor. If the aromat1c sulfonic acid 1s 30 Cm IZOZC too large in quantity, on the other hand, the oxygen content of the composition is insufficient stoichio- 4 30 em 110C metrically and explosive power thereof is lost.

a 28 :8 The organic plasticizer which may be used as one of the main reducing agents is difficultly soluble in' g: 3 28:8 aqueofis hfirog eh peroxide sofution itself. Even if the organic plasticizer is in the form of an emulsion h drophammer test in Table 2 Was ealTied or a dispersion, reactivity thereof with hydrogen according to a method described inDavis' Chemisperoxide is poor and the mixture of them does not try of Powder and Explosives, p. 21, published by exhibit explosive properties. However, if the organic John Wiley & Sons Inc. in 1950. OQtFSiXth plasticizer in the form of a mixture with an aromatic -plosion.point by using a 5. Kg hammer s taken sulfonic acid as in the present invention is mixed drOp hammer sensitivity Valllewith aqueous hydrogen peroxide solution, a homoge- Deeompositio" temperatures Were determined y ;neous solution can be obtained, of which the safety usl'flgadl'fferemielt-helmalahalyzerand stability are increased. The proportion of the same as in Table 2.

, particular stabilizer.

Conventional Compositions N05'- 7 and 8 are highly organic plastieizer to aromatic sulfonic acid is in the Sensitive and y decompose at low temperatures, range of from 120.] to 1:3. As the proportion is handling of them is y dangerous 0n the l' increased, safety and stability are increased, but

agents in the invention is preferably 3-30 percent,

hand, compositions 1 through 6 0f the p i 'explosive power is decreased. The most preferred invention have sufficiently low sensitivities and their; range i rh f 1 5 t 1;2,

decomposition temperatures are high, so they can be' If the aromatic etnreiiie acid' 'a'ii d tlieorganio handled safely. plasticizer are separately mixed with aqueous hydro- Hess brisances of the explosive compositions, gen peroxide solution;along time is required to obtain directly after the preparation and one week therethe organic plasticizer solution, and, further, it is after are shown in Table 3. The compositions are the difficult to obtain a homogeneous solution thereof, as described above. After extensive investigations,

TABLE 3 ,I the inventors have found that a homogeneous solution Hess brisance after Hess brisame afterone can be obtained immediately by previously mixing the- Preparation (m week (mm) aromatic sulfonic acid with the organic plasticizer under heating and then mixing the mixture with aqueous 1 22.0 21.8 2 213 ,5 hydrogen peroxide solutlon. Thus, by preparing an 3 easily soluble fuel mixture previously, it is possible gig 5 3 to obtain the explosive in a simple operation at a 6 20.6 20.5 4 blasting site. The fuel mixture may be prepared by, 7 118 10.5 charging both components in a suitable proportion 8 20.6 15.9 in a mixer provided with a proper stirrer and heater and stirring the whole under heating until a homoge- Hess brisance test of Table 3 was earned out neous solution is obtained. A suitable heating temaccording to Mayers method described in perature range is 70-100C. At higher temperatures, Science of Explosives, p. 375,published by Thomas the components are decomposed and at lower Y. Crowell Company in 1943. Sum of crushing values of the upper and the lower lead columns was taken as value of brisance, by using g of the explosive. As shown in Table 3, the compositions of the invention have excellent storage stability as compared with conventional ones. The explosive power may be kept for at least 2 weeks without using any' mixture may be storedhi a proper container for use prepared instantly at a blasting site.

,In preparing the liquid explosive instantly at a blasting site, aqueous hydrogen peroxide solution in The aqueous hydrogen peroxide solution used as one container is mixed with the aromatic sulfonic mainoxidiging agent of the invention shouldcontaing acid or the mixture of aromatic sulfonic acid and at least percent by weight of hydrogen peroxide, organicplasticizer in another container.

temperatures, a long mixing time is required. To the:

as a starting material when the explosive is to be otherwise the resulting composition has no practical 60 Those containers may be used also for the transexplosive power. If aqueous hydrogen peroxide solu-' portationof the materials from a manufacturing plant tion of a lower'concentration is used, the composi-; to the field. Thus. this is very convenient and highly tion has no efficient explosive power. Efficient, safeuntilthetwocomponents aremixed. concentratlon of hydrogen peroxide in the whole" One of characteristic features of the composicomposition is'in the range of 40-82 percent by tions of the invention is their solubility in water weight and it varies depending upon formulation and in any proportion. Accordingly, it is possible to proportion of other ingredients and aimed properties desensitize the compositions or to convert them of the explosive. Efficient explosive effect cannot be to non-explosive ones by adding a suitable expected outside th1s range. quantity of water to the compositions. The explo- The quantity of the aromatic sulfonic acid used as sive compositions of the invention may be 

2. An explosive composition comprising a mixture of an aqueous hydrogen peroxide solution of a concentration higher than 60 percent by weight, the hydrogen peroxide being more than 40 percent by weight of the explosive composition, an aromatic sulfonic acid, and one or more materials selected from the group consisting of organic plasticizers, water-soluble gelling agents, inorganic oxidizer salts and metal powders.
 3. Explosive composition as set forth in claim 1 comprising a mixture of an aqueous hydrogen peroxide solution of a concentration higher than 60 percent by weight, the hydrogen peroxide being 40 - 82 percent by weight of the explosive composition, and an aromatic sulfonic acid being 3 - 30 percent by weight of said composition.
 4. Explosive composition as set forth in claim 2 comprising a mixture of an aqueous hydrogen peroxide solution of a concentration higher than 60 percent by weight, the hydrogen peroxide being 40 - 82 percent by weight of the explosive composition, an aromatic sulfonic acid being 3 - 30 percent by weight of said composition, and one or more materials selected from the group consisting of organic plasticizer of the weight ratio 1 : 0.1 - 1 : 3 versus said aromatic sulfonic acid, water soluble gelling agent being 2 - 10 percent by weight of said composition, inorganic oxidizer salt being 5 - 30 percent by weight of said composition and metal powder being 1 - 10 percent weight of said composition.
 5. Process for preparing an explosive which comprises heating an organic plasticizer preliminarily to the temperature range 70* -100* C and mixing an aromatic sulfonic acid therewith and then mixing the thus obtained mixture with aqueous hydrogen peroxide solution.
 6. Process for preparing an explosive which comprises heating an organic plasticizer preliminarily to the temperature range 70* -100* C and mixing an aromatic sulfonic acid therewith, then mixing the thus obtained mixture with aqueous hydrogen peroxide solution and with one or more materials selected from the group consisting of water-soluble gelling agent, and inorganic oxidizer salt and metal powder. 